4

Aqueous Reactions
(a) HC 2H302(aq) + KOH(aq) HC 2H302(aq) + OH-(aq) (b)
~
~

Solutions to Exercises

KC 2H30 2(aq) + H 20(1) C 2H302"(aq) H 20(1)

4.40

Cr(OHh(s) + 3HN0 3(aq) ~ Cr(N0 3h(aq) + 3H 20(1)

Cr(OHh(s) + 3H+ (aq)
~

3H 20(1) + Cr 3+(aq)

(c)

Ca(OH)2(aq) + 2HClO(aq) HClO(aq) + OH-(aq)

~

Ca(ClOh(aq) + 2H 20(1)

ClO-(aq) + H 20(1)

4.41

Analyze. Given: names of reactants. Find: gaseous products. Plan. Write correct chemical formulas for the reactants, complete and balance the metathesis reaction, and identify either H 2S or CO 2 products as gases. Solve.

(a)

CdS(s) + H 2S0 4(aq) CdS(s) + 2H+(aq)

~

CdS0 4(aq) + H 2S(g)

H 2S(g) + Cd 2+(aq)

(b)

MgC03(S) + 2HCl0 4(aq) MgC03(S) + 2H+(aq)

~

Mg(Cl0 4h(aq) + H 20(I) + CO 2(g)

H 20(1) + CO 2(g) + Mg 2+(aq)

4.42

(a) (b)

FeO(s) + 2H+(aq) NiO(s) + 2H+ (aq)

~
~

H 20(1) + Fe 2+(aq) H 20(1) + Ni 2+(aq)

4.43

Analyze. Given the formulas or names of reactants, write balanced molecular and net

ionic equations for the reactions.

Plan. Write correct chemical formulas for all reactants. Predict products of the

neutralization reactions by exchanging ion partners. Balance the complete molecular equation, identify spectator ions by recognizing strong electrolytes, write the corresponding net ionic equation (omitting spectators). Solve. (a) CaC0 3(s) + 2HN0 3(aq) ~ Ca(N0 3h(aq) + H 20(I) + CO 2(g)
2H+(aq) + CaC0 3(s) ~ H 20(I) + CO 2(g) + Ca 2+(aq)
(b) FeS(s) + 2HBr(aq)
~

FeBr2(aq) + H 2S(g)

2H+ (aq) + FeS(s) ~ H 2S(g) + Fe 2+(aq)

4.44 K 20(aq) + H 20(I)
~

2KOH(aq), molecular; 02-(aq) + H 20(I)

20H-(aq), net ionic

base: (H+ ion acceptor) 02-(aq); acid: (H+ ion donor) H 20(aq); spectator: K+

Oxidation-Reduction Reactions
4.45 (a) (b) In terms of electron transfer, oxidation is the loss of electrons by a substance, and reduction is the gain of electrons (LEO says GER).: Relative to oxidation numbers, when a substance is oxidized, its oxidation number increases. When a substance is reduced, its oxidation number decreases.

80

4 Aqueous Reactions
4.46

Solutions to Exercises

Oxidation and reduction can only occur together, not separately. When a metal reacts with oxygen, the metal atoms lose electrons and the oxygen atoms gain electrons. Free electrons do not exist under normal conditions. If electrons are lost by one substance they must be gained by another, and vice versa.
Analyze. Given the labeled periodic chart, determine which region is most readily oxidized and which is most readily reduced. Plan. Review the definition of oxidation and apply it to the properties of elements in the indicated regions of the chart. Solve. Oxidation is loss of electrons. Elements readily oxidized form positive ions; these are metals. Elements not readily oxidized tend to gain electrons and form negative ions; these are nonmetals. Elements in regions A, B, and C are metals, and their ease of oxidation is shown in Table 4.5. Metals in region A, Na, Mg, K, and Ca are most easily oxidized. Elements in region D are nonmetals and are least easily oxidized.

4.47

4.48

Elements (metals) from Table 4.5 in region A include Na, Mg. K, and Ca; those from region Care Hg and Au. Let's consider K and Au. Since metals from region A are more readily oxidized than those from region C, K will be oxidized to K+ and Au 3+ will be reduced to Au in the redox reaction. (Choose Au 3 + because it is the Au ion shown in Table 4.5.)
In a balanced redox reaction, the number of electrons lost must equal the number of electrons gained. Since K loses 1 electron in forming K+, while Au 3+ gains 3 electrons when forming Au, 3 K atoms must be oxidized for every 1 Au 3+ that is reduced. This relationship dictates the coefficients in the balanced redox reaction.

3K(s) + Au 3+(aq)
4.49

Au(s) + 3K+(aq)

Analyze. Given the chemical formula of a substance, determine the oxidation number of a particular element in the substance. Plan. Follow the logic in 5ample Exercise 4.8. Solve.

(a)
4.50 4.51
(a)

+4 +4

(b) +4
(b) +2

(c) +7

(d) +1 (d) -2

(e) 0

(f) -1 (022- is peroxide ion) (f) +6

(c) +3

(e) +3

Analyze. Given: chemical reaction. Find: element oxidized or reduced. Plan. Assign oxidation numbers to all species. The element whose oxidation number becomes more positive is oxidized; the one whose oxidation number decreases is reduced. Solve.

~
,

",1:

(a) (b) (c) (d)

4.52

Ni ~ Ni 2+, Ni is oxidized; Cl 2 ~ 2Cl-, Cl is reduced Fe 2+ ~ Fe, Fe is reduced; Al ~ AP+, Al is oxidized Cl 2 ~ 2Cl, CI is reduced; 21- ~ 12, I is oxidized
5 2 ~ 50 4 2-(5, +6),5 is oxidized; H 20 2 (0, -1) ~ H 20 (0, -2); 0 is reduced acid-base reaction oxidation-reduction reaction; Fe is reduced, C is oxidized

'~
1,\"
II

'"I,

(a) (b)

81

4 Aqueous Reactions
(c) (d)
4.53

Solutions to Exercises

precipitation reaction oxidation-reduction reaction; Zn is oxidized, N is reduced

Analyze. Given: reactants. Find: balanced molecular and net ionic equations. Plan. Metals oxidized by H+ form cations. Predict products by exchanging cations and balance. The anions are the spectator ions and do not appear in the net ionic equations. Solve.

(a)

Mn(s) + H 2S0 4(aq) ~ MnS04(aq) + H 2(g); Mn(s) + 2H+(aq)

Mnv'(aq) + H 2(g)

Products with the metal in a higher oxidation state are possible, depending on reaction conditions and acid concentration. (b) (c) (d) 2Cr(s) + 6HBr(aq) Sn(s) + 2HCl(aq)
~

2CrBr3(aq) + 3H 2(g); 2Cr(s) + 6H+(aq)

~

2Cr 3+(aq) + 3H 2(g)

SnCl 2(aq) + H 2(g); Sn(s) + 2H+(aq)

Sn 2+(aq) + H 2(g)

2AI(s) + 6HCH0 2(aq) ~ 2AI(CH0 2h(aq) + 3H 2(g);

2AI(s) + 6HCH0 2(aq) ~ 2AI3+(aq) + 6CH0 2"(aq) + 3H 2(g)

4.54

(a) (b)

2HCl(aq) + Ni(s)

NiCl 2(aq) + H 2(g); Ni(s) + 2H+ (aq) ~ Ni 2+(aq) + H 2(g) H 2S0 4(aq) + Fe(s) ~ FeS0 4(aq) + H 2(g); Fe(s) + 2H+(aq) ~ Fe 2+(aq) + H 2(g)
~

Products with the metal in a higher oxidation state are possible, depending on reaction conditions and acid concentration. (c) (d) 2HBr(aq) + Mg(s)
~

MgBr2(aq) + H 2(g); Mg(s) + 2H+(aq)

~

Mg2+(aq) + H 2(g)

2HC 2H302(aq) + Zn(s)

Zn(s) + 2HC 2H30 2(aq) ~

4.55

Zn(C 2H302h(aq) + H 2(g);

Zn 2+(aq) + 2C 2H302"(aq) + H 2(g)

Analyze. Given: a metal and an aqueous solution. Find: balanced equation. Plan. Use Table 4.5. If the metal is above the aqueous solution, reaction will occur; if the aqueous solution is higher, NR. If reaction occurs, predict products by exchanging Solve. cations (a metal ion or H+), then balance the equation.

(a) (b) (c) (d) (e) 4.56 (a) (b) (c) (d) (e)

Fe(s) + Cu(N0 3h(aq)

Fe(N0 3h(aq) + Cu(s)

Zn(s) + MgS0 4(aq) ~ NR Sn(s) + 2HBr(aq)

~

SnBr2(aq) + H 2(g)

H 2(g) + NiCl 2(aq) ~ NR 2AI(s) + 3CoS0 4(aq) ~ AI2(S04h(aq) + 3Co(s) Mn(s) + NiCl 2(aq) ~ MnCl 2(aq) + Ni(s) Cu(s) + Cr(C 2H302)(aq) ~ NR 2Cr(s) + 3NiS0 4(aq) Pt(s) + HBr(aq)
~

Cr2(S04h(aq) + 3Ni(s)

NR

H 2(g) + CuCl 2(aq) ~ Cu(s) + 2HCl(aq)

82

4 Aqueous Reactions
4.57
(a)

Solutions to Exercises

i.

Zn(s) + Cd 2+(aq) -+ Cd(s) + Zn 2+(aq)

ii. Cd(s) + Ni 2+(aq) -+ Ni(s) + Cd 2+(aq) (b) According to Table 4.5, the most active metals are most easily oxidized, and Zn is more active than Ni. Observation (i) indicates that Cd is less active than Zn; observation (ii) indicates that Cd is more active than Ni. Cd is between Zn and Ni on the activity series. Place an iron strip in CdCl 2(aq). If Cd(s) is deposited, Cd is less active than Fe; if there is no reaction, Cd is more active than Fe. Do the same test with Co if Cd is less active than Fe or with Cr if Cd is more active than Fe. Br2 + 2NaI -+ 2NaBr + 12 indicates that Br2 is more easily reduced than 12, Cl 2 + 2NaBr -+ 2NaCl + Br2 shows that Cl 2 is more easily reduced than Br2' The order for ease of reduction is Cl 2 > Br2 > 12, Conversely, the order for ease of oxidation is 1- > Br : > Cl ".
(b)
Ifllll'
I

(c)

4.58

(a)

Since the halogens are nonmetals, they tend to form anions when they react chemically. Nonmetallic character decreases going down a family and so does the tendency to gain electrons during a chemical reaction. Thus, the ease of reduction of the halogen, X 2, decreases going down the family and the ease of oxidation of the halide, X-, increases going down the family. Cl 2 + 2KI -+ 2KCl + 12 ; Br2 + LiCl-+ no reaction
, '

(c)

i~

Solution Composition; Molarity

...

4.59

(a)

Concentration is an intensive property; it is the ratio of the amount of solute present in a certain quantity of solvent or solution. This ratio remains constant regardless of how much solution is present.

(b)

The term 0.50 mol HCl defines an amount (-18 g) of the pure substance HCl. The term 0.50 M HCl is a ratio; it indicates that there are 0.50 mol of HCl solute in 1.0 liter of solution. This same ratio of moles solute to solution volume is present regardless of the volume of solution under consideration. The concentration of the remaining solution is unchanged, assuming the original solution was thoroughly mixed. Molar concentration is a ratio of moles solute to liters solution. Although there are fewer moles solute remaining in the flask, there is also less solution volume, so the ratio of moles solute/solution volume remains the same. The second solution is five times as concentrated as the first. An equal volume of
the more concentrated solution will contain five times as much solute (five times
the number of moles and also five times the mass) as the 0.50 M solution. Thus,
the mass of solute in the 2.50 M solution is 5 x 4.5 g = 22.5 g.
Mathematically:

....

4.60

(a)

(b)

83